Conversion of a AuI Fluorido Complex into an N‐Fluoroamido Derivative: N−F versus Au−N Reactivity

The AuI complex [Au{N(F)SO2Ph}(SPhos)] (SPhos=dicyclohexyl(2′,6′-dimethoxy[1,1′-biphenyl]-2-yl)phosphane) (2) bearing a fluoroamido ligand has been synthesized by reaction of the fluorido complex [Au(F)(SPhos)] (1) with NFSI (NFSI=N-fluorobenzenesulfonimide). A reaction with CO resulted in an unprecedented insertion into the N−F bond at 2. With the carbene precursor N2CH(CO2Et) N−F bond cleavage gave the Au−F bond insertion product [Au{CHF(CO2C2H5)}(SPhos)] (7). The presence of CNtBu led to Au−N cleavage at 2 and concomitant amide formation to give the cationic complex [Au(CNtBu)(SPhos)][N(F)SO2Ph)] (5), which reacted further to give FtBu as well as the cyanido complex [Au(CN)(SPhos)] (6). These results led to the development of a process for the amination of electrophilic organic substrates by transfer of the fluoroamido group NF(SO2Ph)−.Deutsche Forschungsgemeinschaft http://dx.doi.org/10.13039/501100001659Peer Reviewe

Time-Dependent Point Source Search Methods in High Energy Neutrino Astronomy

We present maximum-likelihood search methods for time-dependent fluxes from point sources, such as flares or periodic emissions. We describe a method for the case when the time dependence of the flux can be assumed a priori from other observations, and we additionally describe a method to search for bursts with an unknown time dependence. In the context of high energy neutrino astronomy, we simulate one year of data from a cubic-kilometer scale neutrino detector and characterize these methods and equivalent binned methods with respect to the duration of neutrino emission. Compared to standard time-integrated searches, we find that up to an order of magnitude fewer events are needed to discover bursts with short durations, even when the burst time and duration are not known a priori.Comment: LaTeX; 17 Pages, 4 figures; submitted to Astroparticle Physic

Distribution and Prevalence of Wolbachia Infections in Native Populations of the Fire Ant Solenopsis invicta (Hymenoptera: Formicidae)

Wolbachia are endosymbiotic bacteria that commonly infect arthropods. These bacteria induce a number of phenotypes in their hosts, including cytoplasmic incompatibility, thelytokous parthenogenesis, feminization, and male killing. We surveyed native South American populations of the fire ant Solenopsis invicta Buren for Wolbachia infections by using a diagnostic polymerase chain reaction assay. In addition, we determined the fidelity of vertical transmission of the bacteria from mother to offspring in this species by assaying daughters in 24 simple-family (monogyne) colonies. Infections were common in many parts of the extensive native range of S. invicta. However, the proportion of individuals infected varied greatly among samples, ranging from zero in several populations from the northerly parts of the range to >90% in more southerly populations. Possible explanations for this variation in the prevalence of Wolbachia infections are discussed. A survey of the two social forms of S. invicta from four geographic areas showed that the prevalence of Wolbachia infections consistently was higher in the monogyne form (single queen per colony) than the sympatric polygyne form (multiple queens per colony). One likely explanation for this trend is that the selective regimes acting on Wolbachia in the two forms differ because of the dissimilar reproductive strategies used by each form. Finally, overall transmission efficiency was found to be very high (>99%), making it unlikely that imperfect transmission prevents the spread of the microbe to near fixation in native population

Selective conversion of alcohols in water to carboxylic acids by in situ generated ruthenium trans dihydrido carbonyl PNP complexes

In this work, we present a mild method for direct conversion of primary alcohols into carboxylic acids with the use of water as an oxygen source. Applying a ruthenium dihydrogen based dehydrogenation catalyst for this cause, we investigated the effect of water on the catalytic dehydrogenation process of alcohols. Using 1 mol% of the catalyst we report up to high yields. Moreover, we isolated key intermediates which most likely play a role in the catalytic cycle. One of the intermediates was identified as a trans dihydrido carbonyl complex which is generated in situ in the catalytic process

Dacryocystitis presenting as post-septal cellulitis: a case report

Dacryocystitis is relatively common, the majority of patients present with pre-septal cellulitis and not an orbital abscess due to anatomical barriers. The authors report a case of dacryocystitis presenting as post-septal cellulitis in a postmenopausal lady with an underlying malignancy. Following antibiotic therapy and elective dacryocystorhinostomy the patient is still under follow-up, and has no further recurrence of symptoms. Orbital abscess in postmenopausal women presenting with dacryocystitis should be considered, as prompt recognition and early surgical intervention is required to prevent visual loss

A comparative study of fragment screening methods on the p38α kinase: new methods, new insights

The stress-activated kinase p38α was used to evaluate a fragment-based drug discovery approach using the BioFocus fragment library. Compounds were screened by surface plasmon resonance (SPR) on a Biacore(™) T100 against p38α and two selectivity targets. A sub-set of our library was the focus of detailed follow-up analyses that included hit confirmation, affinity determination on 24 confirmed, selective hits and competition assays of these hits with respect to a known ATP binding site inhibitor. In addition, functional activity against p38α was assessed in a biochemical assay using a mobility shift platform (LC3000, Caliper LifeSciences). A selection of fragments was also evaluated using fluorescence lifetime (FLEXYTE(™)) and microscale thermophoresis (Nanotemper) technologies. A good correlation between the data for the different assays was found. Crystal structures were solved for four of the small molecules complexed to p38α. Interestingly, as determined both by X-ray analysis and SPR competition experiments, three of the complexes involved the fragment at the ATP binding site, while the fourth compound bound in a distal site that may offer potential as a novel drug target site. A first round of optimization around the remotely bound fragment has led to the identification of a series of triazole-containing compounds. This approach could form the basis for developing novel and active p38α inhibitors. More broadly, it illustrates the power of combining a range of biophysical and biochemical techniques to the discovery of fragments that facilitate the development of novel modulators of kinase and other drug targets. ELECTRONIC SUPPLEMENTARY MATERIAL: The online version of this article (doi:10.1007/s10822-011-9454-9) contains supplementary material, which is available to authorized users

Multi-messenger searches via IceCube’s high-energy neutrinos and gravitational-wave detections of LIGO/Virgo

We summarize initial results for high-energy neutrino counterpart searches coinciding with gravitational-wave events in LIGO/Virgo\u27s GWTC-2 catalog using IceCube\u27s neutrino triggers. We did not find any statistically significant high-energy neutrino counterpart and derived upper limits on the time-integrated neutrino emission on Earth as well as the isotropic equivalent energy emitted in high-energy neutrinos for each event